Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

• This invention relates to methylene-substituted heterocyclic compounds which are novel and have utility as insecticides and acaricides.
• the invention also relates to insecticidal and acaricidal compositions, to the use of such compounds and compositions as insecticides and acaricides, to the preparation of such compounds, and to novel intermediates, and their preparation.
• the invention relates in particular to novel heterocyclic compounds having a haloalkylcarbonylmethylene substituent.
• the alkyl group may be linear or branched and may suitably contain 1 to 4 carbon atoms, suitable examples being methyl, ethyl and propyl.
• the substituent groups which are optionally present may be any of those customarily employed in the development of pesticidal compounds, and/or the modification of such compounds to influence their structure/activity, persistence, penetration or other property.
• substituents include halogen, especially fluorine, chlorine, bromine or iodine atoms, and nitro, cyano, hydroxyl, C1 ⁇ 4 alkoxy, C1 ⁇ 4 haloalkoxy, (C1 ⁇ 4 alkoxy)carbonyl groups, amino, C1 ⁇ 4 alkylamino and C1 ⁇ 4 alkylthio groups. It is preferred, however, that alkyl moieties are unsubstituted, or halogen-substituted.
• optional substituents include halogen, especially fluorine, chlorine and bromine atoms, and nitro, cyano, amino, hydroxyl, C1 ⁇ 4 alkyl, C1 ⁇ 4 haloalkyl (especially CF3), C1 ⁇ 4 alkoxy and C1 ⁇ 4 alkylthio groups. 1 to 3 substituents may suitably be employed.
• An acyl group is suitably an optionally substituted alkylcarbonyl group.
• Suitable heteroaryl groups A may include furyl, thiophenyl, pyrazolyl, imidazolyl, pyrrolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, pyrimidinyl, pyrazinyl, pyridyl, oxazolyl, isoxazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl groups.
• Preferred heteroaryl groups A are thiophenyl, pyrazolyl, 1,2,3-triazolyl, pyrazinyl, pyrimidinyl, pyridyl, isoxazolyl, oxazolyl, thiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl.
• a particularly preferred heteroaryl group A is a pyridyl group, especially a pyrid-3-yl group.
• substituents for the heteroaryl group A may include fluoro, chloro, bromo, cyano, nitro, C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, C1 ⁇ 4 alkylthio, C1 ⁇ 4 haloalkyl, C1 ⁇ 4 haloalkoxy, C1 ⁇ 4 haloalkylthio, amino, mono(C1 ⁇ 4 alkyl)amino and di(C1 ⁇ 4 alkyl)amino.
• Preferred optional substituents are fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino or diethylamino.
• a preferred optional substituent is halogen, especially chlorine.
• An especially preferred optionally substituted heteroaryl group A is a 6-chloro-pyrid-3-yl group.
• n 1
• X represents S or NH.
• R represents a bromine or, especially, a chlorine atom or a C1 ⁇ 4 fluoroalkyl, chloroalkyl or fluorochloroalkyl group, especially a C1 ⁇ 2 fluoroalkyl group, preferably trifluoromethyl. Most preferably R represents a chlorine atom.
• the compounds of the general formula I exhibit pesticidal, for example insecticidal or acaricidal, activity. Accordingly the invention also provides a pesticidal composition comprising a compound of the general formula I together with a carrier. The invention further provides the use of a compound or composition according to the invention, as a pesticide. The invention further provides a method of combating pests at a locus, which comprises applying to the locus a pesticidal compound or composition according to the invention.
• a carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, or to facilitate storage, transport or handling.
• a carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating biocidal compositions may be used.
• compositions according to the invention contain 0.5 to 95% by weight of active ingredient.
• Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montomorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; and solid fertilisers, for example superphosphates.
• natural and synthetic clays and silicates for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminiu
• Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosine and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.
• compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
• a carrier which is a surface-active agent facilitates this process of dilution.
• at least one carrier in a composition according to the invention is a surface-active agent.
• the composition may contain at least two carriers, at least one of which is a surface-active agent.
• a surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic.
• suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example p -octylphenol or p -octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or s
• compositions of the invention may for example be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
• Wettable powders usually contain 25, 50 or 75% w of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers.
• Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 0.5-10% w of active ingredient.
• Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-75% w active ingredient and 0-10% w of additives such as stabilisers, surfactants, slow release modifiers and binding agents. The so-called “dry flowable powders" consist of relatively small granules having a relatively higher concentration of active ingredient.
• Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors.
• Suspension concentrates are usually compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as antifreeze agents for water.
• Aqueous dispersions and emulsions for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention.
• the said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like consistency.
• composition of the invention may also contain other ingredients, for example other compounds possessing herbicidal, insecticidal or fungicidal properties.
• the compounds of the present invention appear to have a broad spectrum of insecticidal and acaricidal activity, but show especially interesting activity against house flies and aphids.
• the compounds of general formula II and III are reacted together under basic conditions, to effect elimination of the compound L-H.
• a polar aprotic solvent is preferably employed, for example dimethylformamide.
• the reaction may suitably be effected at a temperature in the range from 0°C to the reflux temperature.
• a strong base is preferably employed, suitably an alkali metal base, for example sodium hydride or potassium carbonate.
• the base is added first, to a compound of general formula II, at a first temperature, and after an interval the compound of general formula III is added, and the reactions suitably proceeds at a second temperature. With some compounds it is found suitable for the first temperature to be -5 to 5°C and the second temperature, 20 to 30°C. With other compounds it is found suitable for the first temperature to be 20 to 30°C and the second temperature to be the reflux temperature.
• Suitable leaving moieties include mesyl and tosyl groups and, especially, halogen atoms, especially chlorine.
• a further aspect of the present invention relates to compounds of the general formula I, as defined above, when prepared by the process defined above.
• R1 and R2 are preferably both ethyl groups.
• An alcohol for example ethanol, is preferably present, as a solvent.
• a small amount of a promotor such as DBU (1,8-diazabicyclo [5.4.0]undec-7-ene may suitably be present.
• the reaction may suitably be carried out at a temperature in the range 0°C to the reflux temperature.
• a halogenated hydrocarbon for example dichloromethane
• an organic solvent/base for example pyridine
• the anhydride is suitably added slowly to the reaction mixture.
• the temperature is suitably not elevated; 0 to 40°C is preferred for most such reactions.
• Compounds of general formula IV may be prepared by reacting the appropriate acid anhydride and orthoacetate compounds together, as described in Examples herein.
• Chlorodifluoroacetic acid anhydride 25.8 g was added to triethyl orthoacetate (9.4 ml) and pyridine (8.1 ml) in dichloromethane (100 ml).
• the product, 1-(chlorodifluoromethylcarbonyl)-2,2-diethoxy ethene was a red liquid (11.2 g), which was used without further purification.
• 3 g was dissolved in ethanol (25 ml), and to this was added 1,3-propanediamine (1.2 ml). The mixture was stirred overnight at ambient temperature.
• Pentafluoropropionic anhydride 23 g was added to triethyl orthoacetate (7.5 ml) and pyridine (6 ml) in dichloromethane (100 ml) keeping the temperature at about 25°C. The reaction mixture was stirred overnight, then washed with water (100 ml), then with saturated sodium bicarbonate solution (100 ml), then with water (100 ml), dried and the solvent removed under vacuum to leave an orange oil (8.0 g), 1-(pentafluoroethylcarbonyl)-2,2-diethoxyethene.
• 3-Aminopropanethiol hydrochloride (2.5 g), 1-(pentafluoroethylcarbonyl)-2,2-diethoxy ethanol (5.0 g) and DBU (3.0 g) were refluxed in ethanol (50 ml) for 24 hours. After removal of the solvent under vacuum the residue was partitioned between dichloromethane (50 ml) and water (50 ml). The organic phase was washed twice with water (2 x 50 ml), dried, and the solvent removed under vacuum.
• Pesticidal activity of compounds of the invention was assessed against various of the following pests:- Spodoptera littoralis (Egyptian cotton leafworm) Aedes aegypti (yellow fever mosquito) Musca domestica (housefly) Acyrthosiphon pisum (pea aphid) Megoura viciae (vetch aphid) Phaedon cochleariae (mustard beetle) Trialeurodes vaporariorum (greenhouse whitefly) Nephotettix cincticeps (green leaf hopper) Nilaparvata lugens (brown rice plant hopper)
• test methods employed for each species appear below.
• solutions or suspensions of test compound were made up over a range of concentrations in water (initially O.1%w) containing 10%w acetone and 0.025%w "TRITON X-100" (trade mark) surface active agent (the condensation product of ethylene oxide with an alkyl phenol).
• surface active agent the condensation product of ethylene oxide with an alkyl phenol.
• Acaricidal activity of the compounds of the aforementioned Examples was assessed, employing eggs of the glasshouse red spider mite, Tetranychus urticae (T.u.), less than 24 hours old, by the following procedure.
• each leaf disc was infested with 10 female adult mites. On the day of the test, the adults were removed, leaving the eggs laid overnight on the discs. The leaf discs were then sprayed with solutions of test compound made up as in Example 10 above, at a rate equivalent to 340 litres per hectare (3.4 x 10 ⁇ 5 m3/m2).
• toxicity index LC50 (chlorfenson) LC50 (test compound) x 100
• Results of the assessments described in Examples 10 and 11 are provided in Table 1.
• a blank square indicates that testing was not carried out.
• the letters B and C indicate that the first test carried out at the initial test concentration of 0.1%wt (1000ppm) gave a mortality assessment of 40-69% and 0-39%, respectively.
• a rating of A would be given.
• Toxicity indices are stated when available.

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• 1994
  • 1994-10-20 EP EP94307711A patent/EP0652215A1/fr not_active Withdrawn

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